US8618007B2 - Fused cast refractory product with a high alumina content - Google Patents

Fused cast refractory product with a high alumina content Download PDF

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US8618007B2
US8618007B2 US12/595,735 US59573508A US8618007B2 US 8618007 B2 US8618007 B2 US 8618007B2 US 59573508 A US59573508 A US 59573508A US 8618007 B2 US8618007 B2 US 8618007B2
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US20100151232A1 (en
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Isabelle Cabodi
Michel H G Gaubil
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C03B5/237—Regenerators or recuperators specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • C03B5/237—Regenerators or recuperators specially adapted for glass-melting furnaces
    • C03B5/2375—Regenerator brick design ; Use of materials therefor; Brick stacking arrangements
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/107—Refractories by fusion casting
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/107—Refractories by fusion casting
    • C04B35/109—Refractories by fusion casting containing zirconium oxide or zircon (ZrSiO4)
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C04B35/657—Processes involving a melting step for manufacturing refractories
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D17/00—Regenerative heat-exchange apparatus in which a stationary intermediate heat-transfer medium or body is contacted successively by each heat-exchange medium, e.g. using granular particles
    • F28D17/02—Regenerative heat-exchange apparatus in which a stationary intermediate heat-transfer medium or body is contacted successively by each heat-exchange medium, e.g. using granular particles using rigid bodies, e.g. of porous material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/04—Constructions of heat-exchange apparatus characterised by the selection of particular materials of ceramic; of concrete; of natural stone
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9692—Acid, alkali or halogen resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the invention relates to a fused cast refractory product with a high alumina content and to the use of said product as an element in the construction of packing for regenerators, in particular in packing for glass furnace regenerators.
  • Refractory products include fused cast products and sintered products.
  • Sintered products are obtained by mixing suitable starting materials, then forming the mixture while green and firing the resulting green body at a temperature and for a time sufficient to sinter the green body.
  • Fused cast products sometimes termed “electrofused products” are obtained by melting a mixture of appropriate starting materials in an electric arc furnace or by using any other technique which is suitable for such products. The fused liquid is then cast into a mold and the product obtained undergoes controlled cooling.
  • regenerators are a succession of chambers fitted with ceramic elements forming packing and allowing heat to be recovered and restored depending on the cycle.
  • hot gases or fumes that derive from an operating furnace enter the packing via the top portion of the regenerator and release their heat energy to the packing.
  • cold air is supplied to the bottom of other packing heated during a preceding cycle to recover heat energy; that hot air leaves from the top of the packing where it is fed to the furnace burners to burn fuel under the best conditions.
  • the elements that constitute the packing carry out that function in alternation and must thus have very good resistance to thermal shock.
  • the ceramic elements constituting the packing can have various shapes and are described in French patents FR 2 142 624, FR 2 248 748, and FR 2 635 372, for example.
  • the fused cast products employed to produce the packing elements are generally of an AZS (alumina-zirconia-silica) or aluminous type compositions.
  • aluminous products Products containing large quantities of alumina, termed “aluminous products” are known to have the best resistance to high temperatures and are thus used mainly in the top portions of the packing.
  • United States patent US-A-2 019 208 filed on Dec. 16, 1933, describes alumina-magnesia refractory products comprising 2% to 10% of magnesia and with good resistance to thermal variations. However, such products suffer from industrial feasibility problems.
  • SEPR produces and markets the product ER5312RX which contains about 87.5% of Al 2 O 3 , 4.5% of Na 2 O and 8% of MgO. Crystallographic analysis of ER5312RX reveals mainly beta triple prime alumina. While that product has excellent resistance to corrosion by alkaline vapors, it would be advantageous if its behavior could be further improved under certain highly demanding operating conditions, in particular in reducing atmospheres, i.e. containing and excess of CO and alkalines, i.e. containing NaOH vapor.
  • FR-A-2 853 897 describes fused cast aluminous refractory products containing 0.4% to 2.5% of magnesia. Such products offer improved resistance to corrosion by alkaline species, but their behavior is still unsatisfactory under certain conditions, in particular under reducing conditions, i.e. containing excess CO and alkalines, i.e. containing NaOH vapor.
  • the present invention aims to satisfy this need.
  • the invention provides a fused cast refractory product having the following mean chemical composition by weight, as percentages by weight based on the oxides:
  • the refractory products of the invention have high resistance to alkaline corrosion and to thermal shocks. They are thus ideal for use in a regenerator for a glass furnace operating under reducing conditions, in particular to constitute elements of the packing.
  • the product in accordance with the invention also includes one or more of the following optional characteristics:
  • the invention also provides a method of producing a refractory product in accordance with the invention, comprising the following steps in succession;
  • the oxides MgO and Al 2 O 3 are added systematically and methodically in such a manner as to guarantee the amounts required to obtain a product in accordance with the invention.
  • the bath of molten material is agitated before being cast into the mold, in particular by the action of an electric arc or by bubbling through an oxidizing gas.
  • the invention also provides the use of a refractory product in accordance with the invention in a regenerator, in particular in a regenerator for a glass furnace, and more particularly as a packing element in a packing of such regenerators.
  • the product in accordance with the invention is used as an element in the part of said packing through which the cooled gases or fumes exit the packing and/or through which air to be heated enters into said packing.
  • the product is used as an element in the lower portion of said packing.
  • the invention provides the use of a refractory product in accordance with the invention as a packing element for a regenerator associated with a soda-lime glass fusion furnace operating under reducing conditions.
  • FIGS. 1 and 2 are perspective views of examples of refractory products of the invention.
  • FIG. 3 is an optical microscope (Reichert Polyvar 2) image of a cross section along the plane P 3 shown in FIG. 1 , at mid-height, from the skin (on the right in FIG. 3 ) towards the core of a refractory product in accordance with the invention, the length of each vertical white line corresponding to 500 micrometers ( ⁇ m); and
  • FIG. 4 is a photograph of a longitudinal section along the plane P 1 shown in FIG. 1 of a refractory product in accordance with the invention, the section passing via the two branches 10 1 and 10 3 , and via the central hub 12 , together with a detail of this photograph.
  • alkaline corrosion means corrosion resulting from the condensation of alkaline gases.
  • An example that may be mentioned is corrosion due to fumes from melting soda-potash glass which, when the sulfur content in the fumes is low and/or the conditions are reducing, give rise to a phenomenon of condensation of species such as NaOH or KOH in the lower portion of the packing. The absence of sulfur or reducing conditions prevents the formation of species such as Na 2 SO 4 or K 2 SO 4 . A phenomenon of liquid phase corrosion of the refractory products is thus observed.
  • impurities means inevitable constituents that are necessarily introduced with the starting materials or that result from reactions with those constituents.
  • the impurities are not necessary constituents but are merely tolerated.
  • Pore size means its maximum dimension. Pore size is measured by analyzing images of the surface of the products.
  • Crystal “size” is defined by its largest dimension measured in the plane of observation of a polished section.
  • the “lower portion” of a regenerator packing means the 5 to 15 lower stages, i.e., the lowest stages, of a packing. In general, the lower portion is considered to be constituted by the 10 lower stages of the packing.
  • the “skin” is the outer portion of the product that is in contact with the mold and which extends over a thickness of about 250 ⁇ m.
  • a “molten material” is a liquid mass.
  • the liquid mass may contain some solid particles, but in a quantity which is not sufficient for them to be able to endow said mass with structure.
  • the quantity of solid particles is less than 5% by weight, most often less than 2% by weight.
  • a product in accordance with the invention may be manufactured using methods in routine use for the manufacture of fused cast refractory ceramics material.
  • the method may comprise above steps a) to c).
  • step a) the starting materials are selected in a manner so as to guarantee the oxide contents in the finished product in accordance with the invention.
  • step b) melting is preferably carried out by the combined action of a fairly long electric arc which does not produce reduction, and stirring encouraging re-oxidation of the products.
  • melting is preferably carried out under oxidizing conditions.
  • an electric arc melting method is used, for example the long arc melting method described in
  • That method consists in using an electric arc furnace in which the arc strikes between the charge and at least one electrode that is separate from the charge, and adjusting the length of the arc so that its reducing action is reduced to a minimum, while maintaining an oxidizing atmosphere above the molten material and agitating said molten material, either by the action of the arc itself or by bubbling through an oxidizing gas (for example air or oxygen).
  • the molten material is then cast into a mold, preferably in a single casting operation.
  • the casting operation preferably lasts less than 30 seconds, more preferably less than 20 seconds, in particular to produce regenerator packing elements. Substantially all of the molten material cast into the mold, generally at least 90%, or even at least 95% by weight, is still molten at the end of the casting operation.
  • the mold is made of metal, and preferably cooled, so as to obtain a high solidification rate and a high gradient of temperature between the core and the exterior surface of the product.
  • Casting a molten material advantageously allows complex shapes to be manufactured; the liquid molten material can fill any recesses that, for example, are destined to produce corrugations or reliefs on the surface of the finished product. Casting a molten material also allows products having several branches to be manufactured.
  • the low viscosity of the molten material means that it can fill the mold properly, completely filling all of the irregularities or recesses of the mold. It is thus advantageously possible to produce portions in relief of small dimensions in reliable manner. Further, the product has a clean shape.
  • a molten material also means that products can be manufactured with low porosity, typically with porosity of less than 30%, preferably less than 25%.
  • Casting a molten material also means that molds can be used that have at least one profile in section that differs from a flared profile or a straight profile. In particular, it means that molds can be used that do not allow the solid product to exit via the opening of the mold through which the molten material was introduced, i.e. molds that are necessarily in a plurality of parts.
  • the mold is in a plurality of parts.
  • the product may be unmolded before the molten material that has been introduced into the mold has solidified completely.
  • cooling and solidification continue more uniformly, optionally in an annealing furnace.
  • unmolding is carried out less than 1 hour, preferably less than 30 minutes, preferably less than 5 minutes after casting the molten material into the mold.
  • the solidification front in a cross sectional plane, preferably has an outline of a shape that is substantially identical to that of the outline of the product, especially at the periphery of the product.
  • the solidification front preferably has a shape that is also cruciform in a transversal cross sectional plane.
  • a rapid cooling in the mold, then a rapid unmolding before complete solidification, preferably less than 5 minutes after casting the molten material into the mold, advantageously leads to the formation of columnar cristals with a preferential orientation in a direction substantially perpendicular to the solidification front, in particular with the above described products comprising several branches.
  • the cavity of the mold used is complementary in shape to the shape of the product that is to be fabricated.
  • the fabricated product is thus monolithic, i.e. it is constituted by a single fused part with no adhesive, no cuts, and no assembly.
  • the product in accordance with the invention may be cruciform, i.e. comprise four branches or “wings”, 10 1 , 10 2 , 10 3 , and 10 4 .
  • the four branches 10 1 , 10 2 , 10 3 , and 10 4 radiate from a central hub 12 of axis X, preferably forming pairs at right angles, branches 10 1 and 10 3 extending in a plane P 1 , and branches 10 2 and 10 4 extending in a plane P 2 that is orthogonal to plane P 1 .
  • an index i is used to generically designate the corresponding portions of the four branches 10 1 : 10 1 , 10 2 , 10 3 , and 10 4 .
  • each branch has the general shape of a rectangular parallelepiped.
  • the side faces 14 i and 16 i of the branches that are to be placed at the interface with the streams of gaseous fluid passing through the regenerator are preferably substantially parallel to the axis X.
  • the length “l” of the branches may be lie in the range 10 mm to 600 mm and the branch length may be different from one branch to another.
  • the length “l 1 ” of branches 10 1 and 10 3 extending in plane P 1 may differ from the length “l 2 ” of branches 10 2 and 10 4 extending in plane P 2 .
  • the length “l 2 ” is preferably more than 1.5 times the length “l 1 ” and/or less than 3 times, or even less than 2.5 times the length “l 1 ”.
  • the ratio between the length “l 2 ” and the length “l 1 ” may be about 2.
  • the cruciform shape described above has proved to be particularly advantageous in facilitating operations of assembling packing, and also in ensuring that the packing is statically stable.
  • the side faces 14 i and 16 i of the various branches are provided with obstacles or “corrugations”, preferably of the type described in EP-A-0 354 844, incorporated by reference.
  • these obstacles can intensify exchanges between the refractory products of the invention and the gases moving in the regenerator.
  • the height “h” of the branches is preferably the same regardless of the branch under consideration. It is preferably in the range 100 mm to 600 mm.
  • the thickness “e” of the branches is preferably identical regardless of the branch under consideration.
  • the thickness “e” is more than 15 mm, more preferably more than 20 mm and/or less than 60 mm, still more preferably less than 50 mm.
  • the top surface 18 and bottom surface 20 of the product in accordance with the invention are substantially parallel and perpendicular to the side faces 14 i and 16 i , and also preferably are substantially perpendicular to the end faces 22 i of the branches 10 i .
  • the product of the invention may have a “double cruciform” shape as shown in FIG. 2 .
  • This shape corresponds to joining, via the end faces 22 k , two of the cruciform products as shown in FIG. 1 .
  • such a product is, however, obtained by molding in a mold with a double cruciform cavity.
  • the product in accordance with the invention may be tubular in shape, the sides of the product defining a shape in cross section, i.e. in a plane perpendicular to the direction of gas flow, that is square, pentagonal, hexagonal, or octagonal, for example.
  • the thickness in cross section is preferably substantially constant along a side of the product.
  • the ratio h/e of the height to the thickness of at least one side, preferably all of the sides of the product and/or of at least one branch, preferably all of the branches, is more than 5, preferably more than 8, more preferably more than 10.
  • the ratio l/e of the length to the thickness of at least one side, preferably all of the sides of the product and/or of at least one branch, preferably all of the branches, is more than 2, preferably more than 3.
  • Table 1 summarizes test results. The test products tested, which are non-limiting, are given with the aim of illustrating the invention.
  • the mixtures of the starting materials were melted using a conventional arc furnace melting method as described, for example, in FR-A-1 208 577 or in FR-A-2 058 527, then cast into a mold (for example using the method described in FR-A-2 088 185) to obtain X4 type parts suitable for acting as regenerator elements.
  • These parts have a four-branched cruciform shape, each branch having a height of 420 mm, a length of 130 mm, and a thickness of 30 mm.
  • Example 1 of Table 1 The part of Example 1 of Table 1 is the product ER1682RX, manufactured and sold by SEPR. It contains about 50% of Al 2 O 3 , 32.0% of ZrO 2 , and 15.6% of SiO 2 . Crystallographic analysis thereof reveals about 47% of corundum, 21% of vitreous phase, and 32% of zirconia.
  • the part of Example 2 of Table 1 is the product ER5312RX mentioned in the introduction of the description.
  • Example 3 contains 97.6% of Al 2 O 3 , 1.7% of MgO, and 0.5% of SiO 2 . Its crystallographic analysis reveals about 6% of spinel, 1% of vitreous phase and 93% of corundum.
  • a feasibility indicator was produced by counting the number of defects (cracks and/or broken corners). Feasibility was considered to be acceptable if one or fewer defects were observed.
  • samples were removed from the cruciform parts and then evaluated using the following test A: the samples were placed in a three meter long flame furnace with a temperature gradient along that length that changed from 1300° C. (burner side) to 700° C. (extraction duct side), and that was intended to reproduce the variation between the bottom and the top of a regenerator packing.
  • the samples were placed in the alkaline species condensation zone.
  • An alkaline solution containing 10% (by weight) of Na 2 SO 4 was continuously injected (one liter per hour) to reproduce the alkaline atmosphere.
  • the letter indicates the visual appearance of the product after the test: S corresponds to swelling (increase in volume of more than 5%) of the sample, F corresponds to the appearance of cracks, and A indicates an absence of swelling or cracking, and thus corresponds to good behavior.
  • ND means “not determined” and corresponds to samples that did not undergo test A.
  • test B The aptitude to thermal variations in a sample is determined using test B that consists in subjecting samples that had already undergone test A to 50 thermal cycles. Each cycle comprised raising the temperature from 900° C. to 1350° C. then returning to 900° C.
  • the letter indicates the visual appearance of the product after the test: D indicates disintegration of the sample, C corresponds to the presence of cracks, and A indicates an absence of cracking and thus corresponds to good behavior.
  • ND means “not determined” and corresponds to samples that did not undergo test B.
  • test C The corrosion resistance of the parts to extreme use and/or over the very long term was determined by quenching samples (dimensions 15 ⁇ 15 ⁇ 100 mm) in pure liquid NaOH at 980° C. (test C).
  • the letter indicates the visual appearance of the product after 20 minutes of the test: I corresponds to an intact sample, D indicates the onset of degradation, and C corresponds to complete destructuring of the material.
  • magnesia content MgO
  • feasibility is no longer guaranteed. This is probably due to the formation of a periclase phase (free magnesia).
  • the feasibility is particularly good for magnesia contents in the range 27.5% to 29%.
  • the products of the invention are the only products to exhibit good behavior for both tests A and C.
  • the remarkable behavior of the products of the invention could be explained by low ionic conductivity, linked to the presence of a large quantity of spinel crystals.
  • the spinel crystals would in fact be chemically transferred less readily than the corundum crystals.
  • the shape of the crystals (columnar crystals) as well as the arrangement of the crystals (overlapping crystals) within the parts would induce excellent cohesion thereof, even after chemical attack.
  • Example 8 The part of Example 8 was sawn along the sectional planes P 1 , at mid-thickness, and P 3 .
  • the photographs of FIGS. 3 and 4 were taken of these sections. The photographs show that the refractory product has a microstructure that is remarkable.
  • the product includes pores 50 that are elongate in shape, termed “tubular”, the total porosity preferably being more than 10% and less than 25%.
  • the diameter of the tubular pores varies from 1 mm to 5 mm in the branches of the product, i.e. away from the shrinkage cavity 52 (which extends substantially along the axis X of a cruciform product such as that of FIG. 1 ) and away from the peripheral zone corresponding to the skin of the product. More than 80% by number of the tubular pores have a diameter of less than 2 mm.
  • the tubular pores have a preferential orientation in a direction substantially perpendicular to the general direction F of the solidification front (and parallel to the direction D of advance of this solidification front).
  • the tubular pores within the branches thus have a preferential orientation in a direction perpendicular to the side faces 16 i of the branches.
  • the tubular pores are distributed throughout the bulk of the branches, except in the zone of the skin. This distribution is substantially homogeneous.
  • FIG. 3 shows that the product includes columnar crystals 60 of spinel. It can be seen that the crystals of columnar spinel have a preferential orientation and extend in the same preferential orientation as the tubular pores 50 , i.e. in a direction substantially perpendicular to the general direction F of the solidification front .
  • the size of the spinel crystals in the branches, away from the skin, is more than 0.1 mm and may attain 15 mm. The size of the spinel crystals increases with distance from the outer surface of the product.
  • FIG. 4 also shows that filling is good, i.e. an absence of voids (a void being an empty space at least one dimension of which is greater than 15 mm), within the part.
  • the porosity of the products of the invention lies in the range 10% to 30% and is distributed in a quasi-uniform manner in the part.
  • the porosity lies in the range 15% to 25%.
  • a porosity of about 20% is considered to be optimal.
  • the pore volume and the homogeneous distribution of this pore volume advantageously allows the products of the invention to effectively accommodate variations in volume due to variations in temperature, even after being subjected to alkaline atmosphere operating conditions.
  • the pores are of small dimensions (of the order of 1 mm to 5 mm in diameter and of the order of 1 mm for the majority of pores).
  • Crystallographic analysis of the products of the invention of Examples 6, 8, and 9 reveals more than 97% of Al 2 O 3 —MgO spinel, the spinel crystals having, away from the skin, a size in the range 100 ⁇ m to 15 mm.
  • Example 13 is mainly constituted by spinel as well as traces of a second phase (periclase). The presence of these two phases is deleterious to feasibility; they behave differently during the cooling phase and may result in cracks.
  • chromium oxide in the presence of alkaline vapors would result in the formation of hexavalent chromium, which is particularly toxic.
  • titanium oxide in the starting materials would result in the formation of an aluminium titanate phase, to the detriment of the spinel phase. This unstable titanate phase would itself result in poor behavior during a thermal cycle.
  • zirconia would result in densification of the product and would not maintain the desired degree of porosity for the products of the invention.
  • the surfaces of a product in accordance with the invention at the interface with gases may exhibit a plurality of obstacles to the flow of the gases, but may also be substantially flat and extend parallel to the flow of the gases.

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FR0754635 2007-04-23
PCT/FR2008/050732 WO2008145924A2 (fr) 2007-04-23 2008-04-22 Produit refractaire pour element d'empilage d'un regenerateur d'un four verrier

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FR2946044B1 (fr) * 2009-06-02 2011-07-01 Saint Gobain Ct Recherches Produit alumine-magnesie pour gazeificateur
JP5657776B2 (ja) 2011-03-11 2015-01-21 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 耐火物、ガラスオーバーフロー成形ブロック、およびガラス体の製造方法
KR20140018935A (ko) 2011-03-30 2014-02-13 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 내화성 물체, 유리 오버플로우 형성 블록, 및 내화성 물체를 형성하고 이용하는 방법
RU2013148633A (ru) * 2011-04-13 2015-05-20 Сэнт-Гобэн Керамикс Энд Пластикс, Инк. Огнеупорное изделие и способ его формования (варианты)
FR2977661B1 (fr) * 2011-07-07 2015-05-08 Saint Gobain Ct Recherches Installation thermique a regenerateur et son procede de fabrication
FR2985007B1 (fr) * 2011-12-22 2014-02-21 Saint Gobain Ct Recherches Regenerateur.
TWI597254B (zh) 2012-01-11 2017-09-01 聖高拜陶器塑膠公司 耐火物件
FR3018804B1 (fr) * 2014-03-18 2016-03-25 Saint Gobain Ct Recherches Grains fondus d'aluminate de magnesium riche en magnesium.
EP3262011A4 (en) 2015-02-24 2018-08-01 Saint-Gobain Ceramics&Plastics, Inc. Refractory article and method of making
US9611178B1 (en) * 2015-09-21 2017-04-04 O'brien Asset Management Regenerative burners having enhanced surface area media
ES2908291T3 (es) * 2016-11-17 2022-04-28 Refractory Intellectual Property Gmbh & Co Kg Producto cerámico refractario, mezcla para la fabricación de un producto de este tipo así como procedimiento para la fabricación de un producto de este tipo

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US9593048B2 (en) 2012-12-19 2017-03-14 Saint-Gobain Centre De Recherches Et D'etudes Europeen Alumina-magnesia product for gasifier or for metallurgical furnace

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